配体诱导的供体态失稳——一种制备全色吸收铜（I）配合物的新途径。
Ligand-Induced Donor State Destabilisation - A New Route to Panchromatically Absorbing Cu(I) Complexes.
作者信息
Tran Jens H, Traber Philipp, Seidler Bianca, Görls Helmar, Gräfe Stefanie, Schulz Martin
机构信息
Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstr. 8, 07743, Jena, Germany.
出版信息
Chemistry. 2022 May 2;28(25):e202200121. doi: 10.1002/chem.202200121. Epub 2022 Mar 25.
The intense absorption of light to covering a large part of the visible spectrum is highly desirable for solar energy conversion schemes. To this end, we have developed novel anionic bis(4H-imidazolato)Cu(I) complexes (cuprates), which feature intense, panchromatic light absorption properties throughout the visible spectrum and into the NIR region with extinction coefficients up to 28,000 M cm . Steady-state absorption, (spectro)electrochemical and theoretical investigations reveal low energy (Vis to NIR) metal-to-ligand charge-transfer absorption bands, which are a consequence of destabilized copper-based donor states. These high-lying copper-based states are induced by the σ-donation of the chelating anionic ligands, which also feature low energy acceptor states. The optical properties are reflected in very low, copper-based oxidation potentials and three ligand-based reduction events. These electronic features reveal a new route to panchromatically absorbing Cu(I) complexes.
对于太阳能转换方案而言，强烈吸收覆盖大部分可见光谱的光非常理想。为此，我们开发了新型阴离子双（4H - 咪唑基）Cu（I）配合物（铜酸盐），其在整个可见光谱及近红外区域具有强烈的全色光吸收特性，消光系数高达28,000 M⁻¹ cm⁻¹。稳态吸收、（光谱）电化学和理论研究揭示了低能量（可见光到近红外）的金属到配体的电荷转移吸收带，这是基于铜的供体状态不稳定的结果。这些高位的基于铜的状态是由螯合阴离子配体的σ-供体作用诱导的，这些配体还具有低能量的受体状态。光学性质反映在非常低的基于铜的氧化电位和三个基于配体的还原事件中。这些电子特性揭示了一种制备全色吸收Cu（I）配合物的新途径。
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